Tetranuclear [Mn2Co2], [Mn2Fe2], and [Mn2Mn2] Complexes with Defective Double-Cubane Cores and Phenoxo and Oxo Bridges: Syntheses, Crystal Structures, and Electronic Properties

Authors

  • Pijush Malpaharia,

    1. Department of Chemistry, Visva Bharati University, Santiniketan 731235, India, www.visvabharati.ac.in
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  • Koushik Pramanik,

    1. Department of Chemistry, Visva Bharati University, Santiniketan 731235, India, www.visvabharati.ac.in
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  • Jean-Pierre Costes,

    1. Laboratoire de Chimie de Coordination du CNRS, 205, route de Narbonne, BP 44099, 31077 Toulouse Cedex 4, France
    2. Université de Toulouse, UPS, INPT, 31077 Toulouse Cedex 4, France
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  • Jean-Pierre Tuchagues,

    Corresponding author
    1. Laboratoire de Chimie de Coordination du CNRS, 205, route de Narbonne, BP 44099, 31077 Toulouse Cedex 4, France
    2. Université de Toulouse, UPS, INPT, 31077 Toulouse Cedex 4, France
    • Jean-Pierre Tuchagues, Laboratoire de Chimie de Coordination du CNRS, 205, route de Narbonne, BP 44099, 31077 Toulouse Cedex 4, France===

      Swapan K. Chandra, Department of Chemistry, Visva Bharati University, Santiniketan 731235, India===

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    • Professor Jean-Pierre Tuchagues passed away suddenly on March 20, 2014

  • Brian Moulton,

    1. Department of Chemistry, University of South Florida, 4202 E. Fowler Avenue, SCA 400, Tampa, Florida 33620, USA
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  • Michael J. Zaworotko,

    1. Department of Chemistry, University of South Florida, 4202 E. Fowler Avenue, SCA 400, Tampa, Florida 33620, USA
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  • Babulal Das,

    1. Department of Chemistry, Indian Institute of Technology, Guwahati 781039, India
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  • Swapan K. Chandra

    Corresponding author
    1. Department of Chemistry, Visva Bharati University, Santiniketan 731235, India, www.visvabharati.ac.in
    • Jean-Pierre Tuchagues, Laboratoire de Chimie de Coordination du CNRS, 205, route de Narbonne, BP 44099, 31077 Toulouse Cedex 4, France===

      Swapan K. Chandra, Department of Chemistry, Visva Bharati University, Santiniketan 731235, India===

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  • Dedicated to the memory of Professor Jean-Pierre Tuchagues

Abstract

Three new tetranuclear complexes [MnIII2CoIII2O2(L)2][ClO4]2 (1), [MnIII2FeIII2O2(L)2][ClO4]2 (2), and [MnIII2MnIII2O2(L)2][MnII(NCS)4] (3) have been synthesized through reactions of the mononuclear [MnIIIL] precursor with the corresponding metal perchlorate under aerobic conditions [H3L = tris(2-salicylaldimine)amine, a condensation product between tris(2-aminoethyl)amine and salicylaldehyde in a 1:3 molar ratio]. These compounds have been characterized by spectroscopic and analytical techniques including single-crystal X-ray structure analysis, electron paramagnetic resonance (EPR) spectroscopy, Mössbauer spectroscopy, and magnetic measurements. The structure of 1 consists of oxo-/phenoxo-bridged CoIII and MnIII centers in a defective double-cubane topology. The molecules of 2 and 3 have similar structures with the CoIII centers changed to FeIII centers in 2 and to MnIII centers in 3. These isostructural complexes have been scrutinized with regard to changes in distortions (distances and angles) of the metal coordination spheres. Magnetic studies indicate that 1, 2, and 3 show predominant antiferromagnetic interactions. Changes in the electronic properties concomitant with changes in the distortions in 1, 2, and 3 are analyzed in terms of magnetostructural correlations.

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